EP2139867B1 - Cocristaux de cyprodinil - Google Patents

Cocristaux de cyprodinil Download PDF

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Publication number
EP2139867B1
EP2139867B1 EP08718898.3A EP08718898A EP2139867B1 EP 2139867 B1 EP2139867 B1 EP 2139867B1 EP 08718898 A EP08718898 A EP 08718898A EP 2139867 B1 EP2139867 B1 EP 2139867B1
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EP
European Patent Office
Prior art keywords
cyprodinil
crystal
acid
ray diffraction
powder
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Not-in-force
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EP08718898.3A
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German (de)
English (en)
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EP2139867A2 (fr
Inventor
Neil George
James Forrest
Pauline Theresa Gavan
Rebecca Claire Burton
Lee Gregory
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Syngenta Ltd
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Syngenta Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One nitrogen atom

Definitions

  • the present invention relates to novel co-crystals of cyprodinil and pyrimethanil and their use in fungicidal compositions, in particular agrochemical compositions.
  • Cyprodinil and pyrimethanil are anilinopyrimidine fungicides and are thought to act by inhibiting the biosynthesis of methionine and the secretion of fungal hydrolytic enzymes.
  • Cyprodinil is used as a foliar fungicide on cereals, grapes, pome fruit, stone fruit, strawberries, vegetables, field crops and ornamentals and as a seed dressing on barley to control a wide range of pathogens such as Tapesia yallundae and T. acuformis, Erysiphe spp., Pyrenophora teres, Rhynchosporium secalis, Botrytis spp., Alternaria spp., Venturia spp.
  • thermodynamically stable forms of cyprodinil exhibit characteristic, but different, melting ranges: form A exhibits between 70 and 72°C and form B between 74 and 76°C.
  • EP 0 655 441 discloses the B form of cyprodinil.
  • the thermodynamic stability of polymorphic forms A and B is enantiotropically related and exhibits a phase transition temperature, which, although sensitive to other conditions, is typically at between 15 and 40°C - certainly within the range of temperature fluctuations that may occur during the processing and storage of agrochemical formulations (typically -10°C and +50°C). Below the phase transition temperature form A is the thermodynamically stable form and above, form B is the thermodynamically stable form.
  • a solid state of cyprodinil may undergo transformation by recrystallisation between the two polymorphic forms leading to the generation of large and undesirable particles, which could, for example, block spray nozzles during application of the product.
  • recrystallisation events mean that it may be difficult to maintain the product as a homogeneous formulation and this may lead to issues during transfer to dilution tanks and in ensuring the correct concentration on dilution. Accordingly, this behaviour currently limits the formulation of cyprodinil to formats in which cyprodinil is solubilised e.g. emulsion concentrates. Similar issues exist with pyrimethanil, which may also crystallise under normal formulation and storage conditions.
  • pyrimethanil is a rather volatile compound. These issues make formulation as, for example, a suspension concentrate difficult and restrict the use or pyrimethanil in certain situations. As such, therefore, these issues mean that problems similar to those seen with cyprodinil occur during formulation, storage and application of pyrimethanil.
  • the present invention provides novel co-crystalline forms of cyprodinil with improved properties as compared to the commercially available versions of this fungicide.
  • the co-crystalline form of cyprodinil and the crystal forming compound may be characterised by a crystal morphology or by selected peaks of the powder X-ray diffraction pattern expressed in terms of 2 theta angles.
  • the present invention provides a co-crystal form of cyprodinil and a co-crystal forming compound which has at least one organic acid functional group, wherein hydrogen bonding occurs between the co-crystal forming compound and cyprodinil and wherein the co-crystal forming compound is benzoic acid and the co-crystal is characterised by a powder X-ray diffraction pattern expressed in terms of 2 theta angles, wherein the powder X-ray diffraction pattern comprise the 2 theta angle values listed in Table 2 with the corresponding d spacing values found in Table 2 and wherein said co-crystal forms white rhombic crystals.
  • this stable form of cyprodinil will allow new solid formulation formats, such as suspension concentrates, suspo-emulsions and wet granulations, to be developed and will lead to potential purity benefits (due to the ability to isolate the solid state rather than a liquid) as well as improved handling characteristics (e.g. reduced toxicity).
  • 'co-crystal means a crystalline material which comprises two or more unique components in a stoichiometric ratio each containing distinctive physical characteristics such as structure, melting point and heat of fusion.
  • the co-crystal can be constructed through several modes of molecular recognition including hydrogen-bonding, II (pi)-stacking, guest-host complexation and Van-Der-Waals interactions. Of the interactions listed above, hydrogen-bonding is the dominant interaction in the formation of the co-crystal, whereby a non-covalent bond is formed between a hydrogen bond donor of one of the moieties and a hydrogen bond acceptor of the other.
  • Preferred co-crystals of the present invention are those where hydrogen bonding occurs between the co-crystal forming compound and the cyprodinil.
  • the co-crystals of the present invention may exist in one or more polymeric forms - as for example, is the case with the cyprodinil-benzoic acid crystals detailed above and in the Examples.
  • a polymorphic co-crystal may contain any molar ratio of cyprodinil to co-former, but typically will be in the range of 5:1 to 1:5.
  • a polymorphic form may also contain a different isomeric ratio.
  • Each polymorphic form can be defined by one or more solid state analytical techniques including single crystal X-ray diffraction, powder X-ray diffraction, DSC, Raman or Infra-red spectroscopy.
  • the molar ratio of cyprodinil to co-crystal forming compound in the co-crystal is in the range of from 5:1 to 1:5. More suitably, the ratio of cyprodinil to co-crystal forming compound in the co-crystal is in the range of from 3:1 to 1:3. Even more suitably, the ratio of cyprodinil to co-crystal forming compound is in the range of 2:1 to 1:1. Most suitably, the ratio of cyprodinil to co-crystal forming compound in the co-crystal is approximately 1:1.
  • the co-crystals of the present invention are formed by contacting the cyprodinil with the co-crystal forming compound. This may be done by (i) grinding two solids together, (ii) melting one or both components and allowing them to recrystallise, (iii) solubilising the cyprodinil and adding the co-crystal forming compound or (iv) solubilising the co-crystal forming compound and adding the cyprodinil. It may also be possible to solubilise the cyprodinil in the co-crystal forming compound and vice versa. Crystallisation is then allowed to occur under suitable conditions.
  • crystallisation may require alteration of a property of the solutions, such as pH or temperature and may require concentration of solute, usually by removal of the solvent and typically by drying the solution. Solvent removal results in the concentration of cyprodinil increasing over time so as to facilitate crystallisation. Once the solid phase comprising any crystals is formed, this may be tested as described herein.
  • the present invention is also related to a process for the production of a co-crystal of the invention comprising
  • Assaying the solid phase for the presence of co-crystals of the cyprodinil and the co-crystal forming compound may be carried out by conventional methods known in the art. For example, it is convenient and routine to use powder X-ray diffraction techniques to assess the presence of the co-crystals. This may be effected by comparing the spectra of cyprodinil, the co-crystal forming compound and putative co-crystals in order to establish whether or not true co-crystals have been formed. Other techniques used in an analogous fashion, include differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and Raman spectroscopy. Single crystal X-ray diffraction is especially useful in identifying co-crystal structures.
  • DSC differential scanning calorimetry
  • TGA thermogravimetric analysis
  • Raman spectroscopy Raman spectroscopy
  • the co-crystals of the invention may be readily incorporated into fungicidal compositions (including agrochemical compositions) by conventional means. Accordingly, the invention also provides a fungicidal composition comprising a co-crystal of the invention as defined above. In one embodiment, the fungicidal composition is an agrochemical composition.
  • the agrochemical compositions comprising the co-crystals of the present invention can be used for the control of plant pathogenic fungi on a number of plant species. Accordingly, the invention also provides a method of preventing/controlling fungal infection on plants or plant propagation material comprising treating the plant or plant propagation material with a fungicidally effective amount of an agricultural composition of the invention.
  • plant propagation material is meant seeds of all kinds (fruit, tubers, bulbs, grains etc), cuttings, cut shoots and the like.
  • the agrochemical compositions of the invention can be used to control, for example, Cochliobolus sativus, Erysiphe spp. including E. graminis, Leptosphaeria nodorum, Puccinia spp., Pyrenophora teres, Pyrenophora tritici-repentis, Rhynchosporium secalis, Septoria spp, Mycosphaerella musicola, Mycosphaerella fijiensis var.
  • Cochliobolus sativus Erysiphe spp. including E. graminis, Leptosphaeria nodorum, Puccinia spp., Pyrenophora teres, Pyrenophora tritici-repentis, Rhynchosporium secalis, Septoria spp, Mycosphaerella musicola, Mycosphaerella fijiensis var.
  • the agrochemical compositions of the present invention are suitable for controlling such disease on a number of plants and their propagation material including, but not limited to the following target crops: cereals (wheat, barley, rye, oats, maize (including field corn, pop corn and sweet corn), rice, sorghum and related crops); beet (sugar beet and fodder beet); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, sunflowers); cucumber plants (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); vegetables (spinach, lettuce, asparagus, cabbages, carrots, eggplants, onions, pepper, tomatoes, potatoes, paprika, okra); plantation crops (bananas, fruit trees, rubber trees, tree nurseries), ornamentals (flowers, shrubs, broad-leaved trees and evergreens, such as conifers); as well as other plants such as vines, bushberries (such as blue
  • ryegrasses Lolium L.
  • ryegrasses such as perennial ryegrass ( Lolium perenne L.) and annual (Italian) ryegrass ( Lolium multiflorum Lam.)) and warm-season turf grasses (for example, Bermudagrasses ( Cynodon L. C. Rich), including hybrid and common Bermudagrass; Zoysiagrasses ( Zoysia Willd .), St. Augustinegrass ( Stenotaphrum secundatum (Walt.) Kuntze); and centipedegrass ( Eremochloa ophiuroides (Munro.) hack.)).
  • Bermudagrasses Cynodon L. C. Rich
  • Zoysiagrasses Zoysia Willd .
  • St. Augustinegrass Stenotaphrum secundatum (Walt.) Kuntze
  • centipedegrass Eremochloa ophiuroides (Munro.)
  • Crops' are to be understood to include those crops that have been made tolerant to pests and pesticides, including herbicides or classes of herbicides, as a result of conventional methods of breeding or genetic engineering.
  • Tolerance to e.g. herbicides means a reduced susceptibility to damage caused by a particular herbicide compared to conventional crop breeds.
  • Crops can be modified or bred so as to be tolerant, for example, to HPPD inhibitors such as mesotrione or EPSPS inhibitors such as glyphosate.
  • the rate at which the agrochemical composition of the invention is applied will depend upon the particular type of fungus to be controlled, the degree of control required and the timing and method of application and can be readily determined by the person skilled in the art.
  • the compositions of the invention can be applied at an application rate of between 0.005 kilograms/hectare (kg/ha) and about 5.0kg/ha, based on the total amount of active fungicide in the composition.
  • An application rate of between about 0.1 kg/ha and about 1.5 kg/ha is preferred, with an application rate of between about 0.3 kg/ha and 0.8 kg/ha being especially preferred.
  • the agrochemical compositions comprising the co-crystals of the invention are applied as a formulation containing the various adjuvants and carriers known to or used in the industry. They may thus be formulated as granules, as wettable powders, as emulsifiable concentrates, as suspension concentrates (including oil dispersions), as powders or dusts, as flowables, as solutions, as suspensions or emulsions, suspo-emulsions or as controlled release forms such as microcapsules.
  • the agrochemical composition of the invention may be formulated as a suspension concentrate, a suspo-emulsion or a wet granulation.
  • formulations are described in more detail below and may contain as little as about 0.5% to as much as about 95% or more by weight of the active ingredient in the form of the co-crystal.
  • the optimum amount will depend on formulation, application equipment and nature of the plant pathogenic fungi to be controlled.
  • Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers.
  • the particles contain the active ingredient retained in a solid matrix.
  • Typical solid matrices include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain about 5% to about 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.
  • Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from about 0.5% to about 95% of the concentrate.
  • Suspension concentrates are formulations in which finely divided solid particles of the active compound are stably suspended.
  • the solid particles may be suspended in an aqueous solution or in an oil (as an oil dispersion).
  • Such formulations include anti-settling agents and dispersing agents and may further include a wetting agent to enhance activity as well an anti-foam and a crystal growth inhibitor.
  • these concentrates are diluted in water and normally applied as a spray to the area to be treated.
  • the amount of active ingredient may range from about 0.5% to about 95% of the concentrate.
  • Granular formulations include both extrudates and relatively coarse particles and may be applied without dilution to the area in which control of plant pathogenic fungi is required or dispersed in a spray tank before application, for example.
  • Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound.
  • Granular formulations for use without dilution normally contain about 5% to about 25% active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.
  • active ingredient content may be increased up to 80%.
  • Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.
  • Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates.
  • Encapsulated droplets are typically about 1 to 50 microns in diameter.
  • the enclosed liquid typically constitutes about 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound.
  • Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores.
  • Granules typically range from 1 millimetre to 1 centimetre and preferably 1 to 2 millimetres in diameter. Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring.
  • Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
  • compositions for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents.
  • Pressurised sprayers wherein the active ingredient is dispersed in finely-divided form as a result of vaporisation of a low boiling dispersant solvent carrier, may also be used.
  • formulations described above include wetting, dispersing or emulsifying agents.
  • examples are alkyl and alkylaryl sulphonates and sulphates and their salts, polyhydric alcohols; polyethoxylated alcohols, esters and fatty amines.
  • These agents when used, normally comprise from 0.1 % to 40% by weight of the formulation.
  • Suitable agricultural adjuvants and carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to those skilled in the art. Suitable examples of the different classes are found in the non-limiting list below.
  • Liquid carriers that can be employed include water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl formamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxi
  • Suitable solid carriers include talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, fuller's earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, lignin and the like.
  • a broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application.
  • the surface-active agents can be anionic, cationic, non-ionic or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes.
  • Typical surface active agents include salts of alkyl sulphates, such as diethanolammonium lauryl sulphate; alkylarylsulphonate salts, such as calcium dodecylbenzenesulphonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub. 18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C.sub.
  • soaps such as sodium stearate
  • alkylnaphthalenesulphonate salts such as sodium dibutylnaphthalenesulphonate
  • dialkyl esters of sulphosuccinate salts such as sodium di(2-ethylhexyl) sulphosuccinate
  • sorbitol esters such as sorbitol oleate
  • quaternary amines such as lauryl trimethylammonium chloride
  • polyethylene glycol esters of fatty acids such as polyethylene glycol stearate
  • block copolymers of ethylene oxide and propylene oxide and salts of mono and dialkyl phosphate esters.
  • adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants, sticking agents, and the like.
  • compositions may contain other fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators, in order to broaden the spectrum of activity.
  • Each of the above formulations can be prepared as a package containing the fungicides together with other ingredients of the formulation (diluents, emulsifiers, surfactants, etc.).
  • the formulations can also be prepared by a tank mix method, in which the ingredients are obtained separately and combined at the grower site.
  • Dust and liquid compositions can be applied by the use of power-dusters, broom and hand sprayers and spray dusters.
  • the formulations can also be applied from airplanes as a dust or a spray or by rope wick applications.
  • Both solid and liquid formulations may also be applied to the soil in the locus of the plant to be treated allowing the active ingredient to penetrate the plant through the roots.
  • the formulations of the invention may also be used for dressing applications on plant propagation material to provide protection against fungus infections on the plant propagation material as well as against phytopathogenic fungi occurring in the soil.
  • the active ingredient may be applied to plant propagation material to be protected by impregnating the plant propagation material, in particular, seeds, either with a liquid formulation of the fungicide or coating it with a solid formulation.
  • plant propagation material in particular, seeds
  • other types of application are also possible, for example, the specific treatment of plant cuttings or twigs serving propagation.
  • the agrochemical compositions and formulations of the present invention are applied prior to disease development. Rates and frequency of use of the formulations are those conventionally used in the art and will depend on the risk of infestation by the fungal pathogen.
  • Powder X-ray diffraction analysis clearly shows that the products bear no resemblance to either of the constituent phases suggesting that a new solid state has been formed.
  • the sample was kept at 50°C for 2 hours and then allowed to cool, and evaporate, before being filtered on a Buchner.
  • the sample was kept at 50°C for 2 hours, then kept at 40°C for an hour, then kept at 30°C for an hour, and then finally kept at 20°C for an hour, before being left overnight in the fridge.
  • the product was then isolated on a Buchner.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyridine Compounds (AREA)

Claims (4)

  1. Co-cristal comprenant du cyprodinil et un composé de formation de co-cristaux qui possède au moins un groupement fonctionnel d'acide organique, caractérisé en ce que des liaisons hydrogène se produisent entre le composé de formation de co-cristaux et le cyprodinil, et caractérisé en ce que le composé de formation de co-cristaux est l'acide benzoïque, et le co-cristal est caractérisé par un diagramme de diffraction de rayons X sur poudre exprimé en termes d'angles 2-thêta, caractérisé en ce que le diagramme de diffraction de rayons X sur poudre comprend les valeurs d'angles 2-thêta 11,201, 11,660, 13,78, 15,050, 18,584, 19,294, 20,793, 23,865, 25,697 et 26,765, avec des valeurs d'espacement d correspondantes de 7,893 Å, 7,584 Å, 6,331 Å, 5,882 Å, 4,771 Å, 4,596 Å, 4,269 Å, 3,726 Å, 3,464 Å et 3,328 Å, respectivement, et caractérisé en ce que ledit co-cristal forme des cristaux rhombiques blancs.
  2. Composition fongicide comprenant le co-cristal selon la revendication 1.
  3. Composition selon la revendication 2, qui est une composition agrochimique.
  4. Méthode de prévention/contrôle d'une infection fongique de plantes, comprenant le traitement de la plante par une quantité efficace sur le plan fongicide d'une composition agricole selon la revendication 3.
EP08718898.3A 2007-03-28 2008-03-27 Cocristaux de cyprodinil Not-in-force EP2139867B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB0706044.5A GB0706044D0 (en) 2007-03-28 2007-03-28 C0-Crystals
PCT/GB2008/001066 WO2008117060A2 (fr) 2007-03-28 2008-03-27 Co-cristaux

Publications (2)

Publication Number Publication Date
EP2139867A2 EP2139867A2 (fr) 2010-01-06
EP2139867B1 true EP2139867B1 (fr) 2014-08-20

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EP08718898.3A Not-in-force EP2139867B1 (fr) 2007-03-28 2008-03-27 Cocristaux de cyprodinil

Country Status (12)

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US (1) US8470832B2 (fr)
EP (1) EP2139867B1 (fr)
JP (2) JP2010522734A (fr)
CN (1) CN101679307B (fr)
AU (1) AU2008231568B2 (fr)
BR (1) BRPI0809090A2 (fr)
CA (1) CA2680511C (fr)
ES (1) ES2513824T3 (fr)
GB (1) GB0706044D0 (fr)
RU (1) RU2470922C2 (fr)
UA (1) UA100238C2 (fr)
WO (1) WO2008117060A2 (fr)

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CN112624918B (zh) * 2020-12-18 2022-02-11 深圳市萱嘉生物科技有限公司 一种壬二酸与有机碱的共晶及其制备方法、应用
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GB0706044D0 (en) 2007-05-09
US8470832B2 (en) 2013-06-25
CA2680511A1 (fr) 2008-10-02
BRPI0809090A2 (pt) 2014-09-09
CA2680511C (fr) 2015-10-06
UA100238C2 (uk) 2012-12-10
AU2008231568B2 (en) 2012-11-08
RU2009139768A (ru) 2011-05-10
WO2008117060A2 (fr) 2008-10-02
JP2014001225A (ja) 2014-01-09
CN101679307A (zh) 2010-03-24
WO2008117060A3 (fr) 2008-12-18
CN101679307B (zh) 2013-10-16
US20100137337A1 (en) 2010-06-03
JP2010522734A (ja) 2010-07-08
RU2470922C2 (ru) 2012-12-27
ES2513824T3 (es) 2014-10-27
EP2139867A2 (fr) 2010-01-06
AU2008231568A1 (en) 2008-10-02

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